JP2020072088A - リチウムに基づく特定の負極及びそのような負極を含むリチウム電気化学的発電機 - Google Patents
リチウムに基づく特定の負極及びそのような負極を含むリチウム電気化学的発電機 Download PDFInfo
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- JP2020072088A JP2020072088A JP2019195126A JP2019195126A JP2020072088A JP 2020072088 A JP2020072088 A JP 2020072088A JP 2019195126 A JP2019195126 A JP 2019195126A JP 2019195126 A JP2019195126 A JP 2019195126A JP 2020072088 A JP2020072088 A JP 2020072088A
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- Prior art keywords
- lithium
- electrochemical generator
- calcium
- negative electrode
- solvents
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 46
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- 239000011575 calcium Substances 0.000 claims abstract description 45
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- USOPFYZPGZGBEB-UHFFFAOYSA-N calcium lithium Chemical compound [Li].[Ca] USOPFYZPGZGBEB-UHFFFAOYSA-N 0.000 claims abstract description 24
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- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
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- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
Description
*電極材料として金属水素化物及びオキシ水酸化ニッケルを用いたNi−MH電気化学的発電機;
*電極材料としてカドミウム及びオキシ水酸化ニッケルを用いたNi−Cd電気化学的発電機;
*電極材料として鉛及び酸化鉛PbO2を用いた鉛−酸電気化学的発電機;並びに
*負極の活物質として金属リチウムを用いたもの等のリチウム電気化学的発電機。
LiMO2
の酸化物を挙げることができ、式中、Mは、Ni、Co、Mn、Al、Mg及びそれらの混合物から選択される元素であり、好ましくはまたMは、Ni、Co、Mn、Al及びその混合物から選択される元素である。
− アルカリ電池のほぼ2倍の動作電圧及び安定した放電電圧;
− 280〜360Wh/kgであってよい単位質量当たりのエネルギー密度(特に円筒型の電池用);
− 低い自己放電(年に数パーセント);
− 数多くの民間分野での応用(マルチメディア、おもちゃ等)。
*任意選択でプロトン伝導性である、フッ素化(コ)ポリマー、例えば:
− フッ素化ポリマー、例えばポリテトラフルオロエチレン(略語PTFEで知られている)、ポリフッ化ビニリデン(略語PVDFで知られている);
− フッ素化コポリマー、例えばポリ(フッ化ビニリデン−co−ヘキサフルオロプロペン)(略語PVDF−HFPで知られている);
− プロトン伝導性フッ素化ポリマー、例えばNafion(登録商標);
*エラストマーポリマー、例えばスチレン−ブタジエンコポリマー(略語SBRで知られている)、エチレンプロピレンジエンモノマーコポリマー(略語EPDMで知られている);
*ポリビニルアルコールファミリーのポリマー;
*セルロースポリマー、例えばカルボキシメチルセルロースナトリウム;及び
*それらの混合物。
− 溶媒として、カーボネート溶媒、エーテル溶媒、アミド溶媒、スルホキシド溶媒、ラクトン溶媒、ラクタム溶媒、ニトリル溶媒、エステル溶媒、スルファイト溶媒、及びそれらの混合物から選択される1種又は複数の有機溶媒;
− 少なくとも1種のリチウム塩;
− 任意選択でリチウム塩以外の添加剤
を含んでいてよい。
− 2原子%又は15原子%のカルシウム含有量を備えたリチウムカルシウム合金のシートからなる負極;
− LiFePO4(例えば90.5質量%の程度)、カーボンブラック(例えば4.5質量%の程度)及びポリマーバインダー、例えばポリフッ化ビニリデン(例えば4.5質量%の程度)を含む混合物を含む正極(この混合物は、集電基板、例えば、アルミニウムストリップ上に堆積されている);
− 前記負極と前記正極の間に配置された多孔質セパレーター(前記セパレーターには、カーボネート溶媒の混合物(例えば、エチレンカーボネート/プロピレンカーボネート/ジメチルカーボネートの三成分混合物)中にリチウム塩LiPF6を含む電解質を含浸させている)
を含む電気化学セルを少なくとも1つ含む、電気化学的発電機である。
− 2原子%又は15原子%のカルシウム含有量を備えたリチウムカルシウム合金のシートからなる負極;
− MnO2(例えば80質量%の程度)、アセチレンブラック(例えば10質量%の程度)及びポリマーバインダー、例えばポリフッ化ビニリデン(例えば10質量%の程度)を含む混合物を含む正極(この混合物は、集電基板、例えば、アルミニウムストリップ上に堆積されている);
− 前記負極と前記正極の間に配置された多孔質セパレーター(前記セパレーターには、カーボネート溶媒の混合物(例えば、エチレンカーボネート/プロピレンカーボネート/ジメチルカーボネートの三成分混合物)中にリチウム塩LiPF6を含む電解質を含浸させている)
を含む電気化学セルを少なくとも1つ含む、電気化学的発電機である。
− 厚さ100μm及び表面積1.54cm2である、直径14mmのディスクからなり、カルシウムを2原子%の程度で含むリチウムカルシウム合金から構成される負極;
− LiFePO4(90.5質量%)、ポリフッ化ビニリデン(5質量%)及びSuper P(登録商標)カーボンブラック(4.5質量%)を含む層から構成される、直径16mmのディスクからなる正極(この層は、厚さ20μmのアルミニウムストリップ上に堆積され、LiFePO4坪量が約30mg/cm2であり、すなわち電池容量は約4.5mAh/cm2である);
− 負極と正極の間にある、直径16 mm及び表面積2cm2のディスクの形態のCelgard 2400(登録商標)セパレーター(前記セパレーターに、EC:PC:DMCの質量比がそれぞれ1/1/3であるカーボネート溶媒混合物及びリチウム塩1M LiPF6からなる電解質を含浸させている)
を含むボタン電池の形態の本発明による第1の電気化学的発電機を示す。
− 厚さ100μm及び表面積1.54cm2である、直径14mmのディスクからなり、カルシウムを2原子%の程度で含むリチウムカルシウム合金から構成される負極;
− MnO2(80質量%)、ポリフッ化ビニリデン(10質量%)及びアセチレンブラック(10質量%)を含む層から構成される、直径16mmのディスクからなる正極(この層は、厚さ20μmのアルミニウムストリップ上に堆積され、二酸化マンガン坪量が5.6〜6.2mg/cm2であり、すなわち電池容量は3.45〜3.81mAhである);
− 負極と正極の間にある、直径16 mm及び表面積2cm2のディスクの形態のCelgard 2400(登録商標)セパレーター(前記セパレーターに、EC:PC:DMCの質量比がそれぞれ1/1/3であるカーボネート溶媒の混合物及びリチウム塩1M LiPF6からなる電解質を含浸させている)
を含むボタン電池の形態の本発明による第1の電気化学的発電機を示す。
Claims (19)
- リチウム電気化学的発電機のための負極であって、活物質としてリチウムカルシウム合金を含み、カルシウムが合金中に2原子%〜34原子%の程度で存在し、厚さが5〜200μmのシート又はプレートの形態である、負極。
- リチウムカルシウム合金である活物質のみからなる、請求項1に記載の負極。
- リチウムカルシウム合金が、リチウム及びカルシウムのみを含む、請求項1又は2に記載の電極。
- リチウムカルシウム合金が、カルシウムを2原子%〜15原子%の程度で含むリチウム合金である、請求項1から3のいずれかに記載の電極。
- リチウムカルシウム合金中のカルシウムが、全体的又は部分的にCaLi2の形態である、請求項1から4のいずれかに記載の電極。
- 自立している、請求項1から5のいずれかに記載の電極。
- 活物質としてリチウム挿入材料を含む正極、負極、及び前記負極と前記正極の間に配置されたリチウムイオンを伝導する電解質を含む電気化学セルを少なくとも1つ含む、電気化学的発電機であって、負極が請求項1から6のいずれかに記載の負極である、電気化学的発電機。
- リチウム挿入材料が、少なくとも1種の遷移金属元素を含むリチウム化酸化物、少なくとも1種の遷移金属元素を含むリチウム化リン酸塩、二酸化マンガン、及びそれらの混合物から選択される、請求項7に記載の電気化学的発電機。
- 少なくとも1種の遷移金属元素を含むリチウム化酸化物が、式:
LiMO2
(式中、Mは、Ni、Co、Mn、Al、Mg及びそれらの混合物から選択される元素である)
の酸化物である、請求項8に記載の電気化学的発電機。 - 少なくとも1種の遷移金属元素を含むリチウム化酸化物が、LiMn2O4等の、スピネル構造を有するリチウム化酸化物である、請求項8に記載の電気化学的発電機。
- 少なくとも1種の遷移金属元素を含むリチウム化リン酸塩が、式LiM1PO4(式中、M1は、Fe、Mn、Co及びそれらの混合物から選択される)の化合物である、請求項8に記載の電気化学的発電機。
- 少なくとも1種の遷移金属元素を含むリチウム化リン酸塩がLiFePO4である、請求項8又は11に記載の電気化学的発電機。
- リチウム挿入材料がMnO2である、請求項8に記載の電気化学的発電機。
- 正極が、少なくとも1種の電子伝導性添加剤及び/又は少なくとも1種のバインダーを含む、請求項7から13のいずれかに記載の電気化学的発電機。
- 電子伝導性添加剤が、カーボンブラック、アセチレンブラック、グラファイト、炭素繊維、カーボンナノチューブ、チタン、ニッケル、アルミニウム、ステンレス鋼、及びそれらの混合物から選択される、請求項14に記載の電気化学的発電機。
- バインダーがポリマーバインダーである、請求項14又は請求項15に記載の電気化学的発電機。
- リチウムイオンを伝導する電解質が、少なくとも1種の有機溶媒及び少なくとも1種のリチウム塩を含む液体電解質である、請求項7から16のいずれかに記載の電気化学的発電機。
- 1種又は複数種の有機溶媒が、カーボネート溶媒、エーテル溶媒、アミド溶媒、スルホキシド溶媒、ラクトン溶媒、ラクタム溶媒、ニトリル溶媒、エステル溶媒、スルファイト溶媒、及びそれらの混合物から選択される、請求項17に記載の電気化学的発電機。
- リチウム塩が、LiPF6、LiClO4、LiBF4、LiAsF6、LiSbF6、LiAlCl4、LiGaCl4、LiCF3SO3、LiC(SO2CF3)3、リチウムビス(トリフルオロメチルスルホニル)イミド、LiN[SO2CF3]2、LiSCN、硝酸リチウムLiNO3、リチウムビス(オキサラト)ボレート、リチウムビス(フルオロスルホニル)イミド、LiPF3(CF2CF3)3、トリフルオロメタンスルホン酸リチウムLiCF3SO3、フルオロスルホン酸リチウムLiSO3F、LiC6F5SO3、LiO3SCF2CF3、LiO2CCF3、LiB(C6H5)4、及びそれらの混合物からなる群から選択される、請求項17又は請求項18に記載の電気化学的発電機。
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US3930888A (en) * | 1973-05-14 | 1976-01-06 | Catalyst Research Corporation | Molten metal anode |
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CA2068290C (fr) * | 1992-05-08 | 1999-07-13 | Michel Gauthier | Prise de contact electrique sur des anodes de lithium |
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